CN107735070B - Powder for forming tooth surface film comprising calcined apatite - Google Patents
Powder for forming tooth surface film comprising calcined apatite Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
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- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/816—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising titanium oxide
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B1/00—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means
- B05B1/30—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to control volume of flow, e.g. with adjustable passages
- B05B1/3006—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to control volume of flow, e.g. with adjustable passages the controlling element being actuated by the pressure of the fluid to be sprayed
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- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
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Abstract
The purpose of the present invention is to provide a powder for film formation using hydroxyapatite as a main component of teeth and hydroxyapatite blended with a color tone adjusting agent, the powder for film formation being suitable for use in an apparatus for forming a film on a tooth surface by spraying the powder onto the tooth surface, thereby forming a film having high hardness and extremely low solubility in acid in a short time and being suitable for forming a film of powder conforming to the color tone of teeth in a short time; in order to achieve the above object, the following powders were produced: sintering the mixture at 600-1350 ℃ in an inert gas atmosphere to obtain hydroxyapatite powder; and powder obtained by applying plasma irradiation or plasma irradiation and mechanical energy to hydroxyapatite powder obtained by sintering at 600-1350 ℃; and a film-forming powder obtained by blending these hydroxyapatite powders with a color tone adjuster.
Description
Technical Field
The present invention relates to: a powder for film formation containing a hydroxyapatite powder as a main component of teeth, which is suitable for use in an apparatus for forming a film on a tooth surface by spraying the powder onto the teeth, and which forms a film having high hardness and extremely low solubility in an acid on the tooth surface in a short time; and a powder for film formation using a hydroxyapatite powder, which is blended with a color tone adjusting agent for adjusting the color tone of a crown, and which is suitable for forming a film conforming to the color tone of a tooth in a short time.
Background
Apatite (particularly, hydroxyapatite) is a main component constituting teeth and bones, has excellent biocompatibility, and is an ideal material for replacing or repairing damaged hard tissues, and therefore, in recent years, development of a dental or medical material containing hydroxyapatite has been advanced. In dentistry, in order to prevent caries, treat caries or bleach teeth, a dentifrice containing hydroxyapatite (patent documents 1 and 2), a glass powder for glass ionomer cement containing hydroxyapatite (patent document 3), and a tooth bleaching agent in which hydroxyapatite powder and a strong acid aqueous solution are mixed and applied in the form of a dental paste (patent document 4) have been developed.
Further, as a method for forming a calcium phosphate compound layer, a plasma spraying method (patent document 5), a sputtering method (patent document 6), and a thermal decomposition method (patent documents 7 and 8) are disclosed, but these methods are not methods capable of directly coating teeth in the mouth.
On the other hand, as a method capable of integrating with enamel and dentin, a device has been proposed in which hydroxyapatite powder, which is a main component of enamel and dentin, is sprayed at high speed onto a tooth surface to form a hydroxyapatite film on the surface of enamel and dentin (patent documents 9 to 12).
It has been known that, even when the technique of spraying a powder as described in the present invention on a target object is used, a layer of hydroxyapatite powder can be formed on a metal surface, and for example, by uniformly coating hydroxyapatite on the surface of an implant, biocompatibility can be further improved, and the technique can sufficiently contribute to prevention of peri-implantitis, long-term stabilization of prognosis of treatment, and improvement of maintainability.
As described above, as a method capable of integrating with enamel and dentin, a method of forming a hydroxyapatite film on the surface of enamel and dentin by spraying hydroxyapatite powder, which is a main component of enamel and dentin, onto the surface of tooth at a high speed has been studied, but the method has not yet reached a practical level, and for example, when a hydroxyapatite film is formed on the surface of enamel and dentin and integrated, film formation efficiency with respect to the amount of powder sprayed is poor, film formation takes a long time, and the formed film has high solubility with respect to acid, and the like.
In addition, in the background of the present invention, in recent years, there has been an increasing demand for a cosmetic dental treatment for patients, and treatments using a bleaching method or a porcelain veneering method are known as a treatment method for a cosmetic dental treatment. On the other hand, when the film formation is performed on the teeth by spraying the hydroxyapatite powder, since the color tone of the crown can be adjusted by the same component as the teeth, healthy dentin is not attacked, and the dentin and the like can be strengthened, and treatment that significantly reduces the burden on the patient can be realized.
However, although there have been proposed proposals concerning an apparatus and a method for forming a hydroxyapatite film on the surface of enamel or dentin by spraying a hydroxyapatite powder onto the surface of a tooth at a high speed, there have been no proposals concerning an apatite powder for forming a film having a high hardness and extremely low solubility to an acid in a short time, or concerning a hydroxyapatite powder as a color tone adjusting material for various kinds of cosmetic treatment in accordance with the color tone of the tooth.
Further, the production method of apatite powder for forming a film having high hardness and extremely low solubility in acid in a short time and the production method of a color tone adjusting material therefor are only produced by ordinary baking, grinding, mixing, and the like, and no detailed study has been made. In particular, in the production method of a color tone adjusting material, production has been conventionally performed by mixing powders with each other using a powder mixer or the like, but it is considered that, in the case of a method using only a mixing operation, if a variation occurs in composition due to insufficient mixing of the powders or the like, the following problem arises: the formed film is uneven in color tone, discolored, or the like.
Further, the vickers hardness of enamel of a tooth is reported from 270 to 366Hv by the research and study committee of dental instruments of the japanese dental institute of dental engineering, and it is also reported that properties of a dental crown restoration need to be equal to or more than physical properties of dentin (non-patent document 1). Further, there are reports relating to plasma irradiation (non-patent documents 2 to 4).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4040705
Patent document 2: japanese patent No. 3971877
Patent document 3: japanese laid-open patent publication No. 672112
Patent document 4: japanese patent No. 3340265
Patent document 5: japanese patent laid-open No. 2014-50610
Patent document 6: japanese patent laid-open publication No. 2005-76113
Patent document 7: japanese laid-open patent publication No. 1-086975
Patent document 8: japanese patent laid-open No. 2001-178813
Patent document 9: japanese patent No. 5031398
Patent document 10: japanese patent No. 3962061
Patent document 11: japanese patent laid-open publication No. 2015-13095
Patent document 12: japanese patent laid-open publication No. 2015-104429
Non-patent document
Non-patent document 1: the committee on research and study of dental materials, "appropriate values of physical and mechanical properties desired for dental restorations" (sexualine permeability adjustment について of physical and mechanical instruments of sequin patent No. に and まれる of family), dental materials and instruments, 16(6), 555-.
Non-patent document 2: in northern wilderness, 5 other people, "open atmospheric plasma" (atmospheric プラズマを point けてみよう), J.plasma Fusion Res.vol.84, No.1,19-28,2008.
Non-patent document 3: chinhai, others 2 people, "atmospheric pressure plasma injection experiment capable of simply triggering" ( に experiment of scheduling of プラズマジェット through められる), Shenu high school research era 50 (2012)
Non-patent document 4: baijisheng, 2 others, "study of atmospheric pressure plasma to study of particle accelerator for scientific education" (study of atmospheric pressure プラズマ to study of particle accelerator for scientific education), and report of results of collective study by science education awarding fund H25 tokyo university of industry, yota prefecture
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a powder for film formation which can rapidly form a film having high hardness and extremely low solubility in an acid on a substrate such as a tooth surface, and can achieve color tone adjustment similar to that of a tooth.
Means for solving the problems
The inventors of the present application have developed the following powder for film formation: a film-forming powder obtained by firing a hydroxyapatite powder using an inert gas; a film-forming powder obtained by adding and mixing a color tone adjuster for adjusting the color tone of a crown to the film-forming powder; by subjecting these film-forming powders to plasma irradiation or mechanical energy such as compression or shearing with a low-temperature plasma treatment apparatus in order to clean and activate the particle surface, a hydroxyapatite film having high strength and low solubility in acid or a hydroxyapatite film having a crown color tone adjustable can be formed on a base material such as a tooth surface in a short time. When the film-forming powder of the present invention is used, a film can be formed in a short time because the film is formed well with respect to the ejection amount of the powder, and the powder is less scattered, and has little adverse effect on a patient and a dentist.
Namely, the present invention is as follows.
(1) Powder for film formation having an average particle diameter of0.5 to 30 μm, wherein the powder is used in a device for spraying teeth to form a film on the surface of teeth, and the powder is prepared by spraying Ca at 600 to 1350 ℃ in an inert gas atmosphere10-X·MX(ZO4)6Y2(wherein X is 0 to 10, M is a metal or hydrogen, ZO4Is PO4、CO3、CrO4、AsO4、VO4、SiO4、SO4Or GeO4Y is hydroxyl, halogen or carbonate) and firing the apatite.
(2) The powder for film formation according to the item (1), wherein the apatite is hydroxyapatite.
(3) The powder for film formation according to the above (1) or (2), wherein the inert gas is argon or nitrogen.
(4) The powder for film formation according to any one of the above (1) to (3), further comprising a color tone adjuster for adjusting the color tone of a crown.
(5) The powder for film formation according to item (4), wherein the color tone adjuster for a dental crown is at least one selected from the group consisting of titanium oxide, zinc oxide, ultramarine blue and red pigments.
(6) The powder for film formation according to any one of the above (1) to (5), wherein the powder for film formation is produced by plasma irradiation.
(7) The powder for film formation according to item (6) above, wherein the powder for film formation is produced by further applying mechanical energy.
(8) The powder for film formation according to the above (7), wherein the powder for film formation is produced by applying mechanical energy and then irradiating plasma.
(9) The film-forming powder according to any one of (6) to (8) above, wherein helium is used as an irradiation gas in the plasma irradiation.
(10) The powder for film formation according to any one of the above (1) to (9), wherein when the powder is sprayed onto a substrate under conditions of a nozzle inner diameter at a tip of a head (hand) of 0.5 to 5.0mm, a spraying pressure of 0.2 to 0.8MPa, a distance between a tip of the spray nozzle and the substrate of 0.1 to 3.0cm, and a moving speed of the spray nozzle of 0 to 10 mm/sec, a film thickness of the formed film is 30 μm or more and a Vickers hardness of 340Hv or more.
(11) A method for producing a powder for film formation having an average particle diameter of 0.5 to 30 [ mu ] m, which is used in a device for spraying a tooth to form a film on the surface of the tooth, characterized in that Ca is applied to the surface of the tooth at 600 to 1350 ℃ in an inert gas atmosphere10-X·MX(ZO4)6Y2(wherein X is 0 to 10, M is a metal or hydrogen, ZO4Is PO4、CO3、CrO4、AsO4、VO4、SiO4、SO4Or GeO4Y is hydroxyl, halogen or carbonate) is fired, and then pulverized and classified.
(12) The method for producing a film-forming powder according to item (11), wherein the apatite is hydroxyapatite.
(13) The method for producing a powder for film formation according to the above (11) or (12), wherein the inert gas is argon gas or nitrogen gas.
(14) The method for producing a film-forming powder according to any one of (11) to (13), wherein a color tone adjuster for adjusting a color tone of a crown is further blended.
(15) The method for producing a film-forming powder according to item (14), wherein the color tone adjuster for a dental crown is at least one selected from the group consisting of titanium oxide, zinc oxide, ultramarine blue and a red pigment.
(16) The method for producing a film-forming powder according to any one of (11) to (15), wherein the powder is subjected to plasma irradiation after pulverization and classification.
(17) The method for producing a powder for film formation according to item (16), wherein mechanical energy is further applied.
(18) The method for producing a powder for film formation according to item (17), wherein the mechanical energy is applied and then plasma irradiation is performed.
(19) The method for producing a film-forming powder according to any one of (16) to (18), wherein helium gas is used as an irradiation gas in the plasma irradiation.
(20) The method for producing a powder for film formation according to any one of the above (11) to (19), wherein when the powder is sprayed onto a substrate under conditions of a head tip nozzle inner diameter of 0.5 to 5.0mm, a spray pressure of 0.2 to 0.8MPa, a spray nozzle tip-substrate distance of 0.1 to 3.0cm, and a spray nozzle moving speed of 0 to 10 mm/sec, a film formed has a film thickness of 30 μm or more and a Vickers hardness of 340Hv or more.
(21) A pellet comprising the film-forming powder according to any one of (1) to (10) above.
Other embodiments of the present invention include: [1]A method for forming a film on a tooth surface by using a powder for film formation obtained by spraying the Ca described above at 600 to 1350 ℃ in an inert gas atmosphere in an apparatus for spraying teeth10-X·MX(ZO4)6Y2A film-forming powder having an average particle diameter of 0.5 to 30 μm, which is produced by firing the apatite; [2]Subjecting the Ca to a treatment at 600 to 1350 ℃ in an inert gas atmosphere10-X·MX(ZO4)6Y2A film-forming powder having an average particle diameter of 0.5 to 30 μm, which is produced by firing the apatite, and which is used as a film-forming powder for forming a film on a tooth surface when used in a device for spraying the powder onto a tooth; [3]Subjecting the Ca to a treatment at 600 to 1350 ℃ in an inert gas atmosphere10-X·MX(ZO4)6Y2Use of a powder having an average particle diameter of 0.5 to 30 μm, which is produced by firing the apatite, for producing a powder for film formation which is used in a device for spraying a tooth to form a film on the surface of the tooth; [4]A powder for film formation having an average particle diameter of 0.5 to 30 μm, the powderThe powder for film formation is characterized in that the powder for film formation is used in a device for spraying teeth so as to form a film on the surface of the teeth, and the powder for film formation is Ca at 600-1350 DEG C10-X·MX(ZO4)6Y2The apatite is produced by firing the apatite and then irradiating the fired apatite with plasma.
Effects of the invention
Since the film-forming powder of the present invention is sprayed at a high speed onto the tooth surface, a apatite film can be formed quickly without placing a burden on the patient, and therefore, caries prevention, caries treatment, tooth bleaching, and cosmetic treatment using a film having a color close to the tooth surface can be easily performed. In addition, since the film formation layer formed only of hydroxyapatite is translucent, when the film is formed on a carious region, a hypersensitive region, a root surface exposed portion, or the like, the surgical site is not easily distinguished, and therefore, it is also important to impart a color tone to the film formation layer in order to clarify the surgical region.
According to the present invention, since inhibition of solubility of the film-forming layer and improvement of hardness are confirmed, the film can be stably maintained for a long period of time, that is, a powder for film formation containing a color tone adjusting agent, which is suitable for obtaining a film in which color unevenness of the film-forming layer is inhibited and color tone is stable, can be obtained. In addition, for a patient who is annoyed by the color tone of the tooth, a film formation layer having various color tones desired by the individual patient can be formed, and the contribution to the cosmetic dental treatment is great.
Drawings
FIG. 1 is a view showing a plasma generator used in the present invention.
FIG. 2 is a diagram showing a high voltage generating circuit in the plasma generating apparatus used in the present invention.
FIG. 3 is a graph showing the average particle diameter and particle size distribution of the hydroxyapatite powder for film formation produced in example 2-1.
FIG. 4 is a diagram showing a diffraction pattern obtained by the powder X-ray diffraction apparatus of example 9-1.
FIG. 5 is a graph showing the change in the spectrum obtained by a laser Raman spectroscopy apparatus of the film-forming powder of example 9-2.
FIG. 6 is a photograph showing a film-forming layer obtained by using a film-forming powder containing a color tone adjusting agent.
FIG. 7 is a photograph showing a multilayer film-forming layer (1% titanium oxide in the 1 st layer, 5% zinc oxide in the 2 nd layer, and hydroxyapatite in the 3 rd layer) obtained by using the film-forming powder produced in example 2 and the film-forming powder containing a color tone adjusting agent.
FIG. 8 is a sectional view of the multilayer film-forming layer shown in FIG. 7, which is taken with a laser microscope.
FIG. 9 is a photograph of a film-forming layer (photo) formed on the surface of a tooth by using the powder for film formation containing the color tone adjusting agent of examples 2 to 4 (containing 1% of titanium oxide (left drawing) and 5% of zinc oxide (right drawing)).
Detailed Description
The powder for film formation of the present invention is a powder having an average particle diameter of 0.5 to 30 [ mu ] m for use in a device for spraying teeth, which is used for forming a film on the surface of teeth, and is characterized in that the powder for film formation is prepared by subjecting Ca to 600 to 1350 ℃ in an inert gas atmosphere10-X·MX(ZO4)6Y2(wherein X is 0 to 10, M is a metal or hydrogen, ZO4Is PO4、CO3、CrO4、AsO4、VO4、SiO4、SO4Or GeO4Y is hydroxyl, halogen or carbonate) and firing the apatite; the method for producing the powder for film formation of the present invention is not particularly limited as long as the Ca is applied at 600 to 1350 ℃ in an inert gas atmosphere10-X·MX(ZO4)6Y2The apatite is sintered, and then pulverized and classified, thereby producing an average particle diameter used in a device for forming a film on a tooth surface by spraying powder to a toothA method of forming a film-forming powder having a particle size of 0.5 to 30 μm; the apatite is preferably a calcium phosphate-based apatite, and among them, those represented by the formula Ca10(PO4)6(OH)2Hydroxyapatite of basic calcium phosphate is shown.
The apatite of the calcium phosphate group is a synthetic apatite having a Ca/P molar ratio of, for example, about 1.4 to 1.8, and is included in the apatite of the present invention, because it exhibits properties of apatite and has an apatite structure even if the Ca/P molar ratio is not 1.67.
The hydroxyapatite is 1 kind of calcium phosphate, has good biocompatibility, and is contained in a large amount in bones, teeth and the like. In addition to hydroxyapatite synthesized by a usual method, it can be obtained from fish bones of edible fish such as salmon, pig bones, cow bones, etc., which are natural hard tissues.
The method for synthesizing hydroxyapatite used in the present invention is not particularly limited, and may be appropriately selected. For example, the salt can be obtained by reacting a calcium salt with a phosphate in an aqueous solution and drying the reaction product at a predetermined temperature. Examples of the calcium salt include common calcium salts such as calcium hydroxide, calcium acetate, calcium carbonate, calcium chloride, calcium citrate, and calcium lactate, and examples of the phosphate include common phosphates such as phosphoric acid, ammonium phosphate, sodium phosphate, potassium phosphate, pyrophosphoric acid, and sodium hexametaphosphate.
Other synthesis methods include the following methods: after dissolving calcium nitrate tetrahydrate in pure water, an aqueous ammonium dihydrogen phosphate solution was slowly added to a solution obtained by adjusting the pH of the solution to 10 with aqueous ammonia, at this time, a small amount of aqueous ammonia was added so that the pH in the solution became 10, an aqueous solution of diammonium hydrogen phosphate was completely added, aging was performed at 90 ℃ while stirring the solution, the precipitate was filtered, washed in pure water by ultrasonic treatment, and the obtained solid was dried at 80 ℃.
Further, the following methods can be mentioned: a phosphoric acid aqueous solution was added dropwise to a 0.5M calcium hydroxide aqueous suspension at room temperature to prepare an apatite suspension, the pH of the reaction solution was adjusted to 10.5 using an aqueous ammonia solution, after confirming that the solutions were completely mixed, the suspension was aged overnight, the obtained precipitate was filtered, and the solid was dried at 80 ℃.
Furthermore, hydroxyapatite can be appropriately synthesized by a usual production method (for example, adding pure water to calcium hydrogen phosphate dihydrate and calcium carbonate, mixing and pulverizing the mixture in an automatic mortar, and drying the resulting mixed powder at 80 ℃).
In the case of synthesizing an apatite in which Y in the above formula is a halogen, when hydroxyapatite is produced, a halogen source such as calcium fluoride, sodium fluoride, or calcium chloride is allowed to coexist, whereby hydroxyl groups of hydroxyapatite can be substituted with halogen, and thus, a fluorapatite Ca in which Y is a halogen can be produced10(PO4)6F2Chlorapatite Ca10(PO4)6Cl2. Alternatively, substitution may be performed by mixing with a solvent containing a halogen source after the formation of hydroxyapatite. Halogen-substituted apatite can also be synthesized by synthesizing hydroxyapatite in a dry state using a halide such as calcium fluoride and a phosphate compound. Fluorine substituted fluorapatite may be used as a tooth surface enhancing agent.
Similarly, when hydroxyapatite is produced, carbonic acid apatite can be synthesized by allowing a carbonate group-containing compound such as carbon dioxide, dry ice, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, ammonium hydrogen carbonate, ammonium carbonate, or calcium carbonate to coexist, and substituting the hydroxyl group of Y with a carbonate group.
Similarly, when Ca is substituted with a metal element, that is, when x in the formula is not 0, in the production of hydroxyapatite, for example, water-soluble salts of sodium, lithium, magnesium, barium, strontium, zinc, cadmium, lead, vanadium, silicon, germanium, iron, arsenic, manganese, aluminum, rare earth elements, cobalt, silver, chromium, antimony, tungsten, molybdenum, and the like coexist, and thereby apatite in which at least a part of Ca is substituted with a metal element can be synthesized.
The film-forming powder of the present invention can be obtained by, for example, firing apatite such as hydroxyapatite produced by the above-described general method at 600 to 1350 ℃, preferably 800 to 1350 ℃, in an inert gas atmosphere. The powder for film formation is obtained by firing at 600 to 1350 ℃ in an inert gas atmosphere, and then pulverizing and classifying (preferably, pulverizing, classifying and mixing) the fired powder to obtain a powder for film formation having an average particle diameter of 0.5 to 30 μm, preferably 1 to 10 μm. The shape, structure and the like are not particularly limited as long as the average particle diameter is 0.5 to 30 μm, and may be appropriately selected according to the purpose. By subjecting the film-forming powder obtained by the above firing to a treatment of plasma irradiation or a treatment of further imparting mechanical energy, a powder more suitable for forming a film can be obtained.
In the powder for film formation of the present invention, it was confirmed that a film can be formed in a short time when the performance of the film formed on a substrate such as a tooth surface is examined, and further, when the hiding power against discoloration of a crown is examined, it is confirmed that a film thickness of 30 μm or more is preferably formed and the Vickers hardness is preferably 340Hv or more, and therefore, it was found that it is necessary to fire apatite at 600 to 1350 ℃ in an inert gas atmosphere. In addition, a color tone adjusting agent for adjusting the color tone of a crown may be blended in the film-forming powder of the present invention. By compounding a hydroxyapatite powder with various color tone modifiers, a film-forming powder containing a color tone modifier for forming a film-forming layer that imparts various colors to teeth can be obtained.
Since the color tone adjuster is used in a small amount, the difference in average particle size does not largely affect the mixability during the mixing with hydroxyapatite, but the particle size of the color tone adjuster is preferably smaller than or approximately the same as the particle size of hydroxyapatite, and therefore, the particle size of the color tone adjuster is preferably 0.01 μm to 30 μm, and more preferably 0.05 μm to 10 μm from the viewpoint of providing more favorable mixability.
As the color tone adjuster for dental crowns, inorganic pigments and organic pigments known for dental use can be used without any limitation. Examples of the inorganic pigment include oxides, hydroxides, sulfides, chromates, silicates, sulfates, carbonates, ferrocyanides, phosphates, and carbon, and among them, oxides are preferably used. Examples of the organic pigment include tar pigments, azo pigments, phthalocyanine pigments, condensed polycyclic pigments, nitro pigments, nitroso pigments, and fluorescent pigments, and among them, azo pigments and phthalocyanine pigments are preferably used. These inorganic pigments and organic pigments may be used in combination.
Specific examples of the white pigment include titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, aluminum oxide, barium sulfate, magnesium fluoride, and the like; examples of the red pigment and/or dye include red oxide, molybdenum red, cromophtal red, red No. 2 (amaranth), red No. 104 (phloxine), red No. 105 (rose bengal), red No. 106 (acid red), red No. 201 (lithol rubine B), red No. 202 (lithol rubine BCA), red No. 203 (lake red C), red No. 204 (lake red CBA), red No. 205 (lithol red), red No. 206 (lithol red CA), red No. 207 (lithol red BA), red No. 208 (lithol red SR), red No. 213 (rhodamine B), red No. 214 (rhodamine B acetate), red No. 215 (rhodamine B stearate), red No. 218 (tetrachloro fluorescein), red No. 219 (brilliant red lake red (briillared) R), red No. 220 (deep maroon)), (deep maroon), Red 221 (toluidine Red), Red 223 (tetrabromofluorescein), Red 225 (sudan III), Red 226 (herrington Pink cn (helindone Pink cn)), Red 227 (Fast Acid Magenta), Red 228 (Permaton Red), Red 230 (1) (eosin YS), Red 230 (2) (eosin YSK), Red 231 (phloxine BK), Red 232 (rose K), Red 401 (violamine R), Red 404 (Fast bright Scarlet), Red 405 (permanent Red F5R), Red 501 (medicinal Scarlet), Red 502 (ponceau 3R), Red 503 (ponceau R), Red 504 (ponceau SX), Red 505 (oil Red), Red 506 (Fast Red S), Red 201 (allersine SS), and Red 401 (allerol 401) Naphthol AS (naphthol rubin), naphthol red FGR, naphthol carmine FBB, naphthol carmine F3B, naphthol red F5RK, naphthol red HF4B), BONA lake (BONA barium lake, BONA calcium lake, BONA strontium lake, BONA manganese lake, BONA magnesium lake), lithol rubin (brilliant carmine 6B), diaminoanthraquinone red, DPP red BO, diketopyrrolopyrrole, perylene red BL, imidazolinone red HFT, imidazolinone carmine HF3C, benzimidazolinone carmine HF4C, diaminoanthraquinone red, dichloroquinacridone, quinacridone magenta, quinacridone red, quinacridone violet, dioxane violet, fused azoscarlet, and the like; in addition, as the yellow pigment and/or dye, examples thereof include Yellow iron oxide, titanium Yellow, chromium oxide, bismuth oxide, cromometta Yellow, Yellow No. 4 (lemon Yellow), Yellow No. 201 (fluorescin), Yellow No. 202 (1) (Fluorescein sodium), Yellow No. 202 (2) (Fluorescein sodium K), Yellow No. 203 (quinoline Yellow WS), Yellow No. 204 (quinoline Yellow SS), Yellow No. 205 (benzidine Yellow G), Yellow No. 401 (hansa Yellow), Yellow No. 402 (prasuvin (Polar Yellow)5G), Yellow No. 403 (1) (naphthol Yellow S), Yellow No. 406 (metalamine Yellow), Yellow No. 407 (fast light Yellow 3G), hansa Yellow 10G, bisazo Yellow (AAMX, AAOT, HR, 4G, 3A, GR, G), benzimidazolone Yellow (H2G, HG), isoindoline Yellow (G, R), pyrazolone Yellow HGR, diarylide Yellow (diarylide Yellow) AAOA, and the like; examples of the blue pigment and/or dye include cobalt blue, ultramarine, prussian blue, claumo blue, phthalocyanine blue, aluminum phthalocyanine blue, indanthrene blue, green No. 3 (fast green FCF), blue No.1 (brilliant blue FCF), blue No. 2 (indigo carmine), blue No. 201 (indigo), blue No. 202 (patent blue NA), blue No. 203 (patent blue CA), blue No. 204 (carbopol threne) blue, blue No. 205 (Alphazurine FG), and the like; examples of the black pigment include black iron oxide and carbon black.
As the color tone adjuster for imparting a glossy feel, silica or fine resin particles (specifically, polymethyl acrylate powder, polyethylene beads, polypropylene beads, polystyrene beads, nylon beads, or the like) can be used.
In addition to the above components, other components (e.g., silica, magnesium phosphate, calcium carbonate, zirconium oxide, etc.) generally used in dental materials may be blended as necessary in the powder for film formation of the present invention within a range that does not impair the effects of the present invention.
The powder for film formation of the present invention may further include: powder with the same average grain diameter or a mixture of powder with different grain diameters; firing the powder with the same inert gas atmosphere, or firing the mixture of powder with different inert gases, or firing the mixture of powder with inert gas and atmosphere; a mixture of powders having different particle diameters and different firing atmospheres; and powders obtained by mixing and firing components other than apatite.
Preferably, the plasma irradiation (in which a device for performing plasma irradiation of low-temperature plasma or the like is used) in the production of the film-forming powder of the present invention is performed not only in the treatment of the apatite powder itself but also in the mixing treatment of the apatite powders with each other or the mixing treatment of the apatite powder with a powder other than apatite such as a color tone adjusting agent. For example, in a method for producing a hydroxyapatite powder containing a color tone adjuster for adjusting the color tone of a crown, it is common to perform a mixing treatment of the hydroxyapatite powder and the color tone adjuster, and in the mixing operation, it is preferable to perform the mixing treatment using an apparatus for performing plasma irradiation of low-temperature plasma or the like.
Preferably, in addition to performing plasma irradiation, the treatment is performed using a device that imparts mechanical energy such as compression and shear. By performing plasma irradiation, the particle surfaces can be cleaned and activated, and by applying mechanical energy, the particles can be firmly and densely combined with each other, and thus, a particle design that further improves the functionality of the powder can be realized. However, it was found that no change in the properties of the formed film was observed even when the film was treated with a device for imparting mechanical energy alone. In addition, by performing a treatment for imparting mechanical energy in addition to the treatment by the above-described plasma irradiation, and particularly by performing a plasma treatment after performing the mechanical energy treatment, it was confirmed that the physicochemical characteristics were changed, for example, crystallization of the particle surface was further improved. The film formed using the powder for film formation of the present invention subjected to the treatment for imparting mechanical energy and the treatment by plasma irradiation showed good results in terms of the characteristics, and it was confirmed that a film suitable for use in an intra-oral environment could be formed.
As the Plasma irradiation device, a Plasma surface treatment device (sugaku corporation), a multi-gas Plasma jet (Plasma Factory), a Plasma mixer pmr (alpha corporation), or the like can be used. Further, by applying mechanical energy such as polishing, friction, stretching, compression, shearing to the particles, changes in structure, phase transition, reactivity, adsorptivity, catalyst activity, and the like can be caused. As the device for applying the mechanical energy, Hybridization System (Nara machine Co., Ltd.), MECHANOFUNSION, Nobilta (Hosokawa Micron) and the like can be used. For example, when MECHANOFUSION is used, the convex portions of the particles are removed by shearing force or the like, and the particles can be polished and reattached to form a chamfered state. By using these apparatuses, a film-forming powder most suitable for forming a film can be produced.
When low-temperature plasma is applied (which promotes cleaning and activation of the particle surface), the applied voltage is preferably set to 5 to 20kV, the rotation speed of the rotor head is preferably set to 1500 to 6000rpm, and the treatment time varies depending on the treatment powder, and may be exemplified by 5 to 20 minutes. As the plasma gas species, helium, argon, oxygen, nitrogen, neon, carbon dioxide, air, and the like can be used, and helium can be preferably exemplified. When the treatment is performed by a device for applying mechanical energy, the rotation speed of the rotor head for applying compression and shear force is preferably set to 100 to 6000rpm, and the treatment time varies depending on the powder to be treated, and may be exemplified by 5 to 30 minutes. The voltage applied to the plasma irradiation apparatus and the mechanical energy applying apparatus, the type of gas, the processing speed, the processing time, and the like can be appropriately changed. The form of the powder for film formation may be not only powder, but also pellets obtained by compacting powder and fired pellets obtained by further firing the compacted powder, and these pellets may be used in the form of powder by crushing, cutting, or the like. The form of the pellet may be a form in which 1 kind of the film-forming powder is formed into a pellet form, or a form in which 2 or more kinds of the film-forming powders are stacked, and these forms are included in the film-forming powder of the present invention for convenience.
The film-forming powder of the present invention can be used for an apparatus for spraying teeth to form a film on the surface of teeth. As the film forming apparatus using powder ejection, the powder ejection apparatuses described in patent documents 9 to 12 and the like can be used. For example, the film forming conditions when using a powder jet apparatus manufactured by this company include a nozzle inner diameter at the tip of the head of 0.5 to 5.0mm, a jet pressure of 0.2 to 0.8MPa, a distance between the tip of the jet nozzle and the tooth surface of 0.1 to 30mm (the tip of the jet nozzle is held perpendicular to the tooth surface), and a jet nozzle moving speed of 0 to 10 mm/sec. The powder injection devices described in patent documents 9 to 12 can be used under the same conditions. The resulting film-forming layer is preferably surface-ground with a diamond grinding Paste (DiaPolisher Paste). Further, after the film is formed using the powder for film formation containing the color tone adjusting agent, a film can be formed using the powder for film formation containing another color tone adjusting agent as an upper layer, or a film can be formed using the powder for film formation containing no color tone adjusting agent, whereby a multi-layered film can be formed on the surface of the dental crown.
The present invention will be described below with reference to examples, but the present invention is not limited to the following examples in any sense.
Example 1
[ Synthesis of apatite ]
Synthesis of 1-hydroxyapatite
A0.3M phosphoric acid aqueous solution (2L) was added dropwise to a 0.5M calcium hydroxide aqueous suspension (2L) at room temperature to prepare an apatite suspension. The pH of the reaction solution was adjusted to 10.5 using an aqueous ammonia solution. After confirming that the solution was completely mixed, the suspension was aged overnight. The resulting precipitate was filtered and the solid was dried at 80 ℃.
Synthesis of 1-2 fluorapatite
An aqueous solution (2L) was prepared by mixing 0.25M calcium hydroxide suspension (2L), 0.3mol phosphoric acid and 0.1mol hydrogen fluoride. To the calcium hydroxide suspension was added dropwise a mixed aqueous solution of phosphoric acid and hydrogen fluoride at room temperature over 2 hours. After completion of the dropwise addition, the suspension was aged at 80 ℃ for 5 hours while being stirred. The resulting precipitate was filtered, and the solid content was dried at 80 ℃.
Synthesis of 1-3-carbonate apatite
Carbon dioxide was bubbled in 0.75L of pure water for 30 minutes. The pH of the solution was lowered from 7 to 4. To the resulting solution was added 0.3mol of phosphoric acid, and the total volume was adjusted to 1L with pure water. This solution was added dropwise to a 0.5M aqueous calcium hydroxide solution (1L) at a rate of 1L/3 h. After stirring the suspension for 2 hours, the suspension was aged overnight, filtered, and the resulting solid was dried at 80 ℃.
Synthesis of 1-4 magnesium solid solution apatite
0.19mol of calcium nitrate tetrahydrate and 0.01mol of Mg (OH) were mixed with 500mL of pure water2And (4) dissolving. Thereafter, the pH of the solution was adjusted to 10 with ammonia water. To this solution was slowly added 0.12M aqueous ammonium dihydrogen phosphate solution (500 mL). At this time, a small amount of ammonia water was added so that the pH in the solution became 10. After the aqueous solution of diammonium hydrogen phosphate was completely added, aging was performed at 90 ℃ for 5 hours while stirring the solution. The precipitate was filtered and washed 3 times with ultrasonic treatment in pure water. The resulting solid was dried at 80 ℃.
Example 2
[ preparation of powder for film formation ]
As the atmosphere furnace for firing, a vacuum replacement type atmosphere furnace 2024-V type (pill-shaped electric apparatus) was used. Further, as a pulverizing and classifying apparatus, a fluidized bed counter jet mill (counter-jet mill)100AFG model (Hosokawa Micron) was used.
2-1 apatite powder for film formation
The synthesized hydroxyapatite, fluorapatite, carbonic apatite and magnesium solid solution apatite are pulverized in a mortar and fired at 200 to 1350 ℃ or 600 to 1350 ℃ in the atmosphere of air, argon gas and nitrogen gas. Crushing and grading the fired samples by using a jet-flow pulverizer, and obtaining hydroxyapatite powder with the average particle size of 0.5-30 mu m from each sample.
2-2 film-forming hydroxyapatite powder containing silica
Further, 1 wt% of silica (as a component other than apatite) was added to the apatite powder for film formation synthesized in 2-1, and the same treatment was performed to obtain a hydroxyapatite powder containing silica. The silica used was "Sakai chemical industry (Corp.) Sciqas series particle size: 1.0 μm ".
2-3 hydroxyapatite powder containing color tone modifier for film formation
A film-forming powder containing a color tone modifier is obtained by blending various color tone modifiers with the hydroxyapatite powder for film formation prepared in the above 2-1. Titanium oxide was obtained using "Kishida chemical (strain): specially prepared ", zinc oxide was prepared using" Hakusui Tec (strain): the Japanese pharmacopoeia zinc oxide (locally acidified type of Ripom) ", the" Pinoa company, Ultramarine "for Ultramarine, and the" Kanto chemical Co., Ltd.: deer grade 1 ", red 204 used" tokyo chemical industry (strain), lake red CBA ".
Example 3
[ plasma irradiation treatment and/or mechanical energy imparting treatment ]
As the plasma irradiation device, a plasma generation device manufactured by this company was used. For the powder mixer used for plasma irradiation, 300cc of a beaker was fixed to an electric turntable type T-AU in an inclined state and used while being rotated.
Fig. 1 and 2 show a plasma generator. In the figure, 1 denotes an AC/DC converter (AC100V → DC24V), 2 denotes a cold cathode tube inverter (DC24V → AC1000V), 3 denotes a booster circuit (cockcroft-walton circuit; AC1000V → AC10KV), 4 denotes a plasma nozzle, and 5 denotes a gas flowmeter. In addition, as a device for applying mechanical energy, MECHANOFUSEON AMS-MINI (Hosokawa micron) was used, and as a device for simultaneously applying mechanical energy and plasma irradiation, NANOCULAR (ナノキュラ) NC-ALB (Hosokawa micron) was used.
3-1 production of powder for film formation treated by plasma irradiation
The hydroxyapatite powder for film formation produced in example 2-1, the hydroxyapatite powder containing silica for film formation produced in example 2-2, and the hydroxyapatite powder containing a color tone adjusting agent for film formation produced in example 2-3 were subjected to plasma irradiation treatment using a plasma generator manufactured by this company. The powder for film formation was subjected to plasma irradiation treatment while mixing the powder for film formation with a mixer (300 cc beaker was rotated by an electric turntable type T-AU), to obtain a powder for film formation subjected to plasma irradiation treatment.
3-2 production of hydroxyapatite powder for film formation treated with plasma irradiation and mechanical energy imparting treatment (Individual treatment)
The hydroxyapatite powder for film formation produced in example 2-1, the hydroxyapatite powder containing silica for film formation produced in example 2-2, and the hydroxyapatite powder containing a color tone modifier for film formation produced in example 2-3 were treated with a device for applying mechanical energy (mechinofusion AMS-MINI, Hosokawa Micron), and then plasma-irradiated to obtain a powder for film formation. Similarly, the hydroxyapatite powder for film formation produced in example 2-1 was subjected to a treatment of plasma irradiation and then treated by a device for applying mechanical energy, to obtain a powder for film formation.
3-3 production of hydroxyapatite powder for film formation treated by plasma irradiation and mechanical energy imparting treatment (Simultaneous treatment)
The hydroxyapatite powder for film formation produced in example 2-1, the hydroxyapatite powder containing silica for film formation produced in example 2-2, and the hydroxyapatite powder containing a color tone adjusting agent for film formation produced in example 2-3 were treated with an apparatus (nanopoclean NC-ALB, Hosokawa Micron) for simultaneously performing the mechanical energy imparting treatment and the plasma irradiation treatment, to obtain a powder for film formation.
3-4 production of hydroxyapatite powder for film formation which has been subjected to mechanical energy imparting treatment
The hydroxyapatite powder for film formation produced in example 2-1, the hydroxyapatite powder containing silica for film formation produced in example 2-2, and the hydroxyapatite powder containing a color tone adjusting agent for film formation produced in example 2-3 were subjected to a mechanical energy treatment to obtain a powder for film formation.
Example 4
[ measurement of film thickness, Ca elution amount, and Vickers hardness ]
The film thickness, the amount of Ca eluted, and the vickers hardness were measured using the hydroxyapatite powder for film formation produced in example 2-1, the hydroxyapatite powder mixed with silica produced in example 2-2, and the hydroxyapatite powder mixed with a color tone adjusting agent produced in example 2-3. Fig. 6 shows a film-forming layer (photograph) obtained using the hydroxyapatite powder for film formation containing the color tone adjuster.
4-1 particle size of powder for film formation
FIG. 3 shows the average particle diameter and particle size distribution of the powder for film formation produced in example 2-1. A particle size distribution measuring apparatus (LA-950, horiba, Ltd.) was used for measuring the particle size distribution of the film-forming powder. In addition, a dry cell (unit) was used for the measurement. In the following "table" and the like, "particle diameter 0.5 μm" means a powder having an average particle diameter of 0.4 to 0.6 μm, "particle diameter 1 μm" means a powder having an average particle diameter of 0.9 to 1.1 μm, "particle diameter 5 μm" means a powder having an average particle diameter of 4.0 to 6.0 μm, "particle diameter 10 μm" means a powder having an average particle diameter of 9.0 to 11.0 μm, "particle diameter 20 μm" means a powder having an average particle diameter of 19.0 to 21.0 μm, and "particle diameter 30 μm" means a powder having an average particle diameter of 29.0 to 31.0 μm.
4-2 film forming method
The smooth enamel surface was cut out from a tooth extracted from a human body, and subjected to surface grinding. The above-mentioned polished surface was subjected to film formation treatment using the above-mentioned various hydroxyapatite powder for film formation with the aid of a film formation apparatus using powder spraying. The film forming conditions were set as the inner diameter of the nozzle at the nose end: 5.0mm, injection pressure: 0.6 MPa. The distance between the tip of the spray nozzle and the substrate was set to 0.5cm (the tip of the spray nozzle was kept perpendicular to the substrate), and the moving speed of the spray nozzle was set to 10 mm/sec. The resulting film-forming layer was surface-polished with a diamond polishing paste. It was confirmed that the thickness of the film-forming layer obtained by the polishing treatment was not changed by using a digital microscope VHX-1000(Keyence corporation).
4-3 measurement of film formation thickness
For the measurement of the film thickness formed by the film formation process of 4-2, the film thickness was obtained by 3D measurement using a digital microscope VHX-1000 (Keyence).
4-4 measurement of Ca elution amount from Membrane
The sample surfaces other than the film formation surface (window of about 2 mm. times.2 mm) subjected to the film formation treatment of 4-2 above were masked with nail polish (nail enamel) to prepare enamel blocks (enamel blocks) for measuring the amount of Ca elution. For the evaluation of the Ca elution amount of the film, the concentration of Ca ions eluted from the film-forming layer was measured by a pH cycle test simulating the pH fluctuation in the oral cavity. As the test solution, 0.2mol/L lactic acid buffer solution (pH4.5) and 0.02mol/L HEPES buffer solution (pH7.0) were used. In this solution, the enamel block prepared above for measuring the elution amount of Ca ions was immersed in a lactic acid buffer solution under test conditions of 37 ℃ for 30 minutes. Next, the substrate was immersed in a HEPES buffer solution for 90 minutes, and the above-described cycles were performed for a total of 3 cycles. After the completion of the test, the concentration of Ca ions eluted into the solution was measured by ion chromatography (cation chromatography). The measurement method was performed under the following measurement conditions.
Device name: intellient HPLC LC-2000Plus (Japan Spectroscopy Co., Ltd.)
Column for measurement: cation measuring column IC YK-421(Shodex Co.)
Eluent: 5mM tartaric acid +1mM dipicolinic acid +1.5g/L boric acid
Flow rate: 1.0 ml/min
Sample introduction amount: 20 μ l
Column temperature: 40 deg.C
A detector: conductivity detector
Measurement of 4-5 Vickers hardness
The film prepared by the film forming treatment was measured using a microhardness meter FM-700(Future Tech Inc.) under conditions of an indentation load of 100g and a load retention time of 30 seconds.
Example 5
[ measurement result 1]
The apatite powder for film formation produced in example 2 was subjected to film formation treatment, and the film formation thickness, Ca elution amount, and vickers hardness were measured for each sample. In the film formation process, a powder spray apparatus manufactured by this company was used. The powder injection device manufactured by this company includes an AC/DC converter (AC100V → DC24V), an electromagnetic valve, a spray separator, an air conditioner, a speed controller, and the like.
5-1 film thickness
The apatite powder for film formation produced in example 2-1 was subjected to film formation treatment, and the film formation thickness was measured. The measurement results of the film thickness of the hydroxyapatite powder obtained by firing at 200 to 1350 ℃ in the air atmosphere are shown in [ table 1], the measurement results of the film thickness of the hydroxyapatite powder obtained by firing at 600 to 1350 ℃ in the argon atmosphere are shown in [ table 2], the measurement results of the film thickness of the hydroxyapatite powder obtained by firing at 600 to 1350 ℃ in the nitrogen atmosphere are shown in [ table 3], and the measurement results of the film thickness of the fluorapatite powder obtained by firing at 600 to 1350 ℃ in the air atmosphere are shown in [ table 4 ].
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
From the above results, it is understood that the film thickness of the hydroxyapatite powder or fluorapatite powder having an average particle size of 0.5 μm, which is obtained by firing at 600 ℃ in an atmospheric atmosphere, is less than 30 μm, but the hydroxyapatite powder having an average particle size of 0.5 to 30 μm, which is obtained by firing at 600 to 1350 ℃ in an argon atmosphere or a nitrogen atmosphere, has a film thickness of 30 μm or more. From this fact, it is found that when a hydroxyapatite powder produced by firing in an inert gas atmosphere, particularly an argon atmosphere, is used as a film-forming powder, a film thickness superior to that in an atmospheric atmosphere can be obtained.
5-2 amount of Ca eluted
The hydroxyapatite powder for film formation produced in example 2-1 was subjected to film formation treatment, and the amount of Ca eluted was measured. The measurement results of Ca elution amounts for various particle diameters of hydroxyapatite powder fired at 600 to 1350 ℃ in an atmospheric atmosphere are shown in [ table 5], the measurement results of Ca elution amounts for various particle diameters of hydroxyapatite powder fired at 600 to 1350 ℃ in an argon atmosphere are shown in [ table 6], and the measurement results of Ca elution amounts for various particle diameters of hydroxyapatite powder fired at 600 to 1350 ℃ in a nitrogen atmosphere are shown in [ table 7 ].
[ Table 5]
[ Table 6]
[ Table 7]
From the above results, it is found that the amount of Ca eluted at the time of film formation using hydroxyapatite powder having an average particle size of 0.5 to 30 μm, which is obtained by firing at 600 to 1350 ℃ in an atmosphere of argon or nitrogen, is reduced as compared with the amount of Ca eluted at the time of film formation using hydroxyapatite powder having an average particle size of 0.5 to 30 μm, which is obtained by firing at 600 to 1350 ℃ in an atmosphere of air. From this fact, it is found that when hydroxyapatite powder produced by firing in an inert gas atmosphere, particularly an argon atmosphere, is used as the film-forming powder, Ca elution amount can be suppressed by about 20% as compared with the case of using the powder in an atmospheric atmosphere.
5-3 Vickers hardness
The hydroxyapatite powder for film formation produced in example 2-1 was subjected to film formation treatment, and the vickers hardness was measured. The measurement results of the vickers hardness of the hydroxyapatite powder fired at 600 to 1350 ℃ in the atmosphere at various particle diameters are shown in [ table 8], the measurement results of the vickers hardness of the hydroxyapatite powder fired at 600 to 1350 ℃ in the argon atmosphere at various particle diameters are shown in [ table 9], and the measurement results of the vickers hardness of the hydroxyapatite powder fired at 600 to 1350 ℃ in the nitrogen atmosphere at various particle diameters are shown in [ table 10 ].
[ Table 8]
[ Table 9]
[ Table 10]
From the above results, it is found that the Vickers hardness of the hydroxyapatite powder having an average particle diameter of 0.5 to 30 μm, which is obtained by firing at 600 to 1350 ℃ in an atmospheric atmosphere, is 302 to 330Hv or less, and all of them are 330Hv or less. This value is a value comparable to the low level of vickers hardness reported in the literature for enamel. On the other hand, the film-forming method is characterized in that the Vickers hardness of hydroxyapatite powder with the average particle size of 0.5-30 μm obtained by sintering the hydroxyapatite powder in an argon atmosphere and a nitrogen atmosphere at 600-1350 ℃ is 351-391 Hv and 341-372 Hv respectively, and is more than 340 Hv. This value is shown as a high level of vickers hardness of enamel reported in the literature, or a value greater than this, showing a tendency to have higher vickers hardness than natural dentin. As described above, it is found that when a hydroxyapatite powder produced by firing in an inert gas atmosphere, particularly an argon atmosphere, is used as a film-forming powder, the vickers hardness can be increased by about 15 to 18% as compared with that in an atmospheric atmosphere.
From the above, it is found that all the measurement results of the film thickness, Ca elution amount, and vickers hardness of the film obtained by film formation using a powder having an average particle size of 0.5 to 30 μm were the most favorable for the hydroxyapatite powder fired at 600 to 1350 ℃ in an inert gas atmosphere, particularly in an argon atmosphere, and the powder was effective as a powder for film formation.
The Vickers hardness of a film formed from a hydroxyapatite powder fired at 600 to 1350 ℃ in an atmospheric atmosphere is 330Hv or less, but the Vickers hardness of a film formed from a hydroxyapatite powder fired at 600 to 1350 ℃ in an inert gas atmosphere is 340Hv or more at any particle diameter, and is a powder effective as a film-forming powder.
Particularly, the best results were obtained for all the measurement results of the film thickness, Ca elution amount, and Vickers hardness of the hydroxyapatite powder obtained by firing at 600 to 1350 ℃ in an argon atmosphere, wherein the film was formed from a powder having an average particle size of 0.5 to 30 μm.
5-4 film thickness (with color tone regulator)
The hydroxyapatite powder containing the color tone adjusting agent for film formation produced in examples 2 to 3 was subjected to film formation treatment, and the film formation thickness was measured. The measurement results of the film thickness of the hydroxyapatite powder containing 1 mass% of titanium oxide, which was obtained by firing at 200 to 1350 ℃ in an argon atmosphere, at various particle diameters are shown in [ table 11], and the measurement results of the film thickness of the hydroxyapatite powder containing 5 mass% of zinc oxide, which was obtained by firing at 200 to 1350 ℃ in an argon atmosphere, at various particle diameters are shown in [ table 12 ].
[ Table 11]
[ Table 12]
From the above results, it is understood that a film (film thickness: 30 μm or more) having high shielding property can be formed in a short time by firing a powder having an average particle diameter of 0.5 to 30 μm at 600 to 1350 ℃ in an argon atmosphere. Comparing the results shown in [ table 11] and [ table 12] with the results shown in [ table 2], it was found that the film thickness when the film was formed using the hydroxyapatite powder containing 5 mass% of zinc oxide was approximately the same as the film thickness when the film was not formed using zinc oxide, and that the film thickness when the film was formed using the hydroxyapatite powder containing 1 mass% of titanium oxide was rather more excellent than the film thickness when the film was not formed using titanium oxide.
Example 6
[ measurement results 2]
The apatite powder for film formation produced in example 2 was subjected to a mechanical energy imparting treatment and then to a plasma irradiation treatment, or an untreated powder in which the mechanical energy imparting treatment and the plasma irradiation treatment were not applied was subjected to a film formation treatment, and the film formation thickness, Ca elution amount, and vickers hardness were measured for each sample. In the method for forming the film, an enamel smooth surface was cut out from a tooth extracted from a human body and subjected to surface polishing in the same manner as in example 4-2. The above-described polished surface was subjected to film formation treatment using various hydroxyapatite powders with the aid of a film formation apparatus using powder spraying. In addition, the film forming conditions are set as follows: 3.0mm, injection pressure: 0.4MPa, the distance between the tip of the spray nozzle and the substrate was set to 10mm (the tip of the spray nozzle was kept perpendicular to the substrate), and the moving speed of the spray nozzle was set to 2 mm/sec. The resulting film-forming layer was surface-polished with a diamond polishing paste.
6-1 plasma irradiation treatment after mechanical energy imparting treatment
For the mechanical energy imparting treatment, a device for applying mechanical energy (MECHANOFUSETON AMS-MINI, Hosokawa Micron) was used, and the treatment was performed for 30 minutes with the rotor speed set at 500 rpm. In the plasma treatment, the container containing the powder after the mechanical energy treatment was rotated at a rotor speed of 150rpm, and plasma under plasma generation conditions (applied voltage of 20kV) was irradiated from the tip of the plasma nozzle for 5 minutes. Helium, argon, nitrogen, carbon dioxide, oxygen are used as the plasma gas.
(1) Hydroxyapatite powder having a particle size of 1 μm obtained by firing in an argon atmosphere
The hydroxyapatite powder having a particle size of 1 μm obtained by firing at 600 to 1350 ℃ in an argon atmosphere produced in example 2-1 was subjected to a mechanical energy imparting treatment and then to a plasma irradiation treatment, and the measurement results of the film thickness of the film formed from the obtained powder were shown in [ table 13], the measurement results of the Ca elution amount in [ table 14], and the measurement results of the vickers hardness in [ table 15], respectively, depending on the type of the plasma gas.
[ Table 13]
[ Table 14]
[ Table 15]
From the above results, it is understood that the film formed from the powder obtained by performing the mechanical energy imparting treatment and then performing the plasma irradiation treatment is superior to the film formed from the untreated powder in all of the items of the film thickness, Ca elution amount, and vickers hardness. Further, the order of the degree of excellence in the influence of the plasma gas species is He>Ar>N2>CO2>O2。
(2) 1: 1 mixed powder of argon atmosphere sintering and atmosphere sintering
The measurement results of the film thickness of the film formed from the obtained mixed powder were shown in [ table 16], the measurement results of the Ca elution amount [ table 17], and the measurement results of the vickers hardness [ table 18], respectively, in accordance with the type of plasma gas, by subjecting a 1: 1 mixed powder of hydroxyapatite powder having a particle size of 1 μm obtained by firing in an argon atmosphere and hydroxyapatite powder having a particle size of 1 μm obtained by firing in an atmospheric atmosphere to a mechanical energy imparting treatment and then to a plasma irradiation treatment.
[ Table 16]
[ Table 17]
[ Table 18]
From the above results, it is understood that the film formed from the mixed powder subjected to the mechanical energy imparting treatment and then the plasma irradiation treatment is excellent in all of the film thickness, Ca elution amount, and vickers hardness, as compared with the film formed from the untreated powder. Further, the effect of the plasma gas species was not different in film thickness, and He was excellent in the order of Ca elution amount>Ar>CO2>N2>O2In terms of Vickers hardness, the order of excellence is He>Ar>N2>CO2>O2。
(3) 1: 1 mixed powder of argon atmosphere firing and nitrogen atmosphere firing
The mechanical energy imparting treatment was performed on a 1: 1 mixed powder of a film-forming powder having a particle size of 1 μm obtained by firing in an argon atmosphere and a film-forming powder having a particle size of 1 μm obtained by firing in a nitrogen atmosphere, and then the plasma irradiation treatment was performed, and the results of measuring the film thickness of a film formed using the obtained mixed powder are shown in [ table 19], the results of measuring the amount of Ca elution are shown in [ table 20], and the results of measuring the vickers hardness are shown in [ table 21], respectively, in accordance with the type of plasma gas.
[ Table 19]
[ Table 20]
[ Table 21]
From the above results, it is understood that the film formed using the mixed powder obtained by subjecting the raw powder to the plasma irradiation treatment after the mechanical energy imparting treatment is used as compared with the film formed using the untreated powderThe film formed was excellent in all of the film thickness, Ca elution amount, and vickers hardness. Further, He is excellent in film thickness with respect to the influence of the plasma gas species, and He is excellent in the order of the degree of the excellent in Ca elution amount>Ar>CO2>N2>O2In terms of Vickers hardness, the order of excellence is He>Ar>N2>CO2>O2. Further, the 1 to 1 mixed powder fired in an argon atmosphere and a nitrogen atmosphere is more excellent in all items of film thickness, Ca elution amount, and vickers hardness than the 1 to 1 mixed powder fired in an argon atmosphere and an atmosphere.
6-2 plasma irradiation treatment (with color tone adjusting agent)
The hydroxyapatite powder blended with a color tone adjusting agent for film formation produced in examples 2 to 3 was subjected to a mechanical energy imparting treatment and then to a plasma irradiation treatment, and the powder thus obtained and untreated powder were used to form a film, and the film thickness, the amount of Ca ion elution from the film, and the vickers hardness of the film were measured. For the mechanical energy treatment, a mechanical energy applying device (MECHANOFUSETON AMS-MINI, Hosokawa Micron) was used, and the treatment was performed for 5 minutes with the rotor speed set at 5,000 rpm. In the plasma treatment, the vessel containing the powder after the mechanical energy treatment was rotated at a rotor speed of 150rpm, and plasma under plasma generation conditions (applied voltage of 5kV) was irradiated from the tip of the plasma nozzle for 20 minutes. Helium, argon, nitrogen, carbon dioxide, oxygen are used as the plasma gas.
In the method for forming the film, an enamel smooth surface was cut out from a tooth extracted from a human body and subjected to surface polishing in the same manner as in example 4-2. The above-described polished surface was subjected to film formation treatment using various hydroxyapatite powders with the aid of a film formation apparatus using powder spraying. In addition, the film formation conditions were set as follows: 0.5mm, injection pressure: 0.2MPa, the distance between the tip of the spray nozzle and the substrate was set to 30mm (the tip of the spray nozzle was kept perpendicular to the substrate), and the moving speed of the spray nozzle was set to 5 mm/sec. The resulting film-forming layer was surface-polished with a diamond polishing paste.
The film-forming powder having an average particle size of 1 μm obtained by firing in an argon atmosphere was mixed with 1 mass% of titanium oxide as a color tone modifier, the film-forming powder thus obtained was subjected to a mechanical energy imparting treatment and then to a plasma irradiation treatment, and the results of measuring the film thickness of the film formed from the obtained powder were shown in [ table 22], the results of measuring the amount of Ca elution were shown in [ table 23] and the results of measuring the vickers hardness were shown in [ table 24] respectively in accordance with the type of plasma gas. Similarly, a film-forming powder having an average particle size of 1 μm obtained by firing in an argon atmosphere was mixed with 5 mass% of zinc oxide as a color tone adjusting agent, the film-forming powder thus obtained was subjected to a mechanical energy imparting treatment and then to a plasma irradiation treatment, and the results of measuring the film thickness of a film formed from the obtained powder, respectively, are shown in [ table 25], the results of measuring the amount of Ca elution are shown in [ table 26] and the results of measuring the vickers hardness are shown in [ table 27 ].
[ Table 22]
[ Table 23]
[ Table 24]
[ Table 25]
[ Table 26]
[ Table 27]
From the above results, it is understood that the film formed by the powder subjected to the plasma irradiation treatment after the mechanical energy imparting treatment is excellent in all of the film thickness, Ca elution amount, and vickers hardness for any plasma gas type, as compared with the film formed by the untreated powder. Further, it is found that, in example 6-2, as in example 6-1, particularly by using helium gas as a plasma gas, the film thickness formation rate was also high, the Ca elution amount was also suppressed, and high vickers hardness was also obtained, and therefore, a stable film having further densification could be formed.
Further, from the above results, it was found that the vickers hardness of the film formed from the film-forming powder subjected to the mechanical energy treatment and the plasma treatment and the film-forming powder containing the color tone adjusting agent was 380Hv or more, and particularly, the vickers hardness of the film formed from the film-forming powder subjected to the plasma treatment after the mechanical energy treatment was 400Hv or more, and therefore, it was confirmed that natural dentin could be reinforced, which is a great advantage in terms of increasing the life of teeth. Further, it was found that the film thickness formed by the film-forming powder containing the color tone adjusting agent, which had been subjected to the mechanical energy treatment and the plasma treatment, was almost not different from the film thickness formed by the film-forming powder, and therefore the color tone adjusting agent did not affect the film formation.
Further, the amount of Ca elution of the film formed from the powder for film formation which has been subjected to the mechanical energy treatment and the plasma treatment and the powder for film formation which contains the color tone adjusting agent shows a lower value than the amount of Ca elution in the case of being formed under the conditions of no treatment (only mixing) or the mechanical energy treatment, and the stability of the formed film is improved, and a dense film having high acid resistance can be obtained.
Further, as a result of examining the ability to conceal discoloration of the crown, it was found that a film thickness of 30 μm or more is preferably formed, and therefore, a film-forming powder capable of forming a film thickness of 30 μm or more in a short time and capable of forming a film having a vickers hardness of 340Hv (which is a moderate level of vickers hardness of enamel) or more can be obtained.
Example 7
[ measurement result 3]
[ difference in Effect due to methods for treating powders having different firing atmospheres ]
7-1 Experimental conditions
The following powders were used for film formation treatment, and the film formation thickness, Ca elution amount, and vickers hardness were measured for each sample: the apatite powder for film formation produced in example 2 was subjected to 1) a treatment of applying mechanical energy and then performing plasma irradiation (mechanical energy → plasma treatment; separate treatment), 2) treatment to apply mechanical energy after plasma irradiation (plasma treatment → mechanical energy; separate treatment), 3) a treatment of simultaneously applying mechanical energy and plasma irradiation (mechanical energy — plasma treatment; simultaneous treatment), 4) treatment by plasma irradiation (plasma treatment), 5) treatment by applying mechanical energy (mechanical energy treatment); and 6) powders (untreated) that are subjected only to firing, pulverization, classification, mixing without plasma irradiation and/or application of mechanical energy treatment. The film thickness, Ca elution amount, and vickers hardness were measured in the same manner as in example 5.
For the mechanical energy imparting treatment, a mechanical energy imparting device (MECHANOFUSETON AMS-MINI, Hosokawa Micron) was used to perform the treatment for 10 minutes while setting the rotor speed to 2500 rpm. In the plasma irradiation treatment, plasma under plasma generation conditions (applied voltage 10kV, plasma gas: helium) was irradiated from the tip of a plasma nozzle while a container containing the powder before and after the mechanical energy application treatment was rotated at a rotor speed of 150rpm, and the treatment was carried out for 10 minutes.
In the method for forming the film, an enamel smooth surface was cut out from a tooth extracted from a human body and subjected to surface polishing in the same manner as in example 4-2. The above-mentioned polished surface was subjected to film formation treatment using various hydroxyapatite powders and hydroxyapatite powder mixed with a color tone adjusting agent by means of a film forming apparatus using powder jet. In addition, the film forming conditions are set as follows: 1.8mm, injection pressure: 0.5MPa, the distance between the tip of the spray nozzle and the substrate was set to 5mm (the tip of the spray nozzle was kept perpendicular to the substrate), and the moving speed of the spray nozzle was set to 1 mm/sec. The resulting film-forming layer was surface-polished with a diamond polishing paste.
Hydroxyapatite powder obtained by sintering in 7-2 argon atmosphere
The film formation treatment 1) to 6) was performed on the film formation powder obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill, and the obtained powder was used to form a film. The results on the film thickness are shown in [ Table 28] to [ Table 30], the results on the Ca elution amount are shown in [ Table 31] to [ Table 33], and the results on the Vickers hardness are shown in [ Table 34] to [ Table 36 ].
[ Table 28]
[ Table 29]
[ Table 30]
[ Table 31]
[ Table 32]
[ Table 33]
[ Table 34]
[ Table 35]
[ Table 36]
From the above results, it is understood that, compared with the film formation using 5) the powder subjected to the mechanical energy imparting treatment and 6) the untreated powder, the film formation using 1) the powder subjected to the plasma irradiation treatment after the mechanical energy imparting treatment, 2) the powder subjected to the mechanical energy imparting treatment after the plasma irradiation treatment, 3) the powder subjected to both the mechanical energy imparting treatment and the plasma irradiation treatment, and 4) the powder subjected to the plasma irradiation treatment is excellent in all items of the film thickness, the Ca elution amount, and the vickers hardness regardless of the particle diameter, and the order of the degree of the excellence is substantially 1) >2) >3) >4) >5) > 6).
7-3 apatite powder for film formation
The same test as that of 7-2 was conducted on fluoroapatite, carbonic acid apatite and magnesium solid solution apatite synthesized in example 2. As a result, in the case of performing the treatment by plasma irradiation (plasma treatment), the treatment by applying both mechanical energy and plasma irradiation, and particularly the treatment by plasma irradiation after the treatment by applying mechanical energy (mechanical energy → plasma treatment (separate treatment)), the film-forming powder obtained was similar to the case of 7-2 in film thickness, Ca elution amount and vickers hardness, as compared with the film-forming powder obtained by merely performing firing, pulverizing, classifying and mixing without performing plasma irradiation and the treatment by applying mechanical energy (untreated).
7-4 argon atmosphere sintering and atmosphere sintering 1: 1 mixed hydroxyapatite powder
The hydroxyapatite powder for film formation obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill and the hydroxyapatite powder obtained by firing in an atmospheric atmosphere and pulverizing and classifying the powder by a jet mill were mixed in a ratio of 1: 1, the same test as that of 7-2 was carried out. The results on the film thickness are shown in [ Table 37] and [ Table 38], the results on the amount of Ca eluted are shown in [ Table 39] and [ Table 40], and the results on the Vickers hardness are shown in [ Table 41] and [ Table 42 ].
[ Table 37]
[ Table 38]
[ Table 39]
[ Table 40]
[ Table 41]
[ Table 42]
From the above results, it is understood that, compared with the film formation using 5) the powder subjected to the mechanical energy imparting treatment and 6) the untreated powder, the film formation using 1) the powder subjected to the plasma irradiation treatment after the mechanical energy imparting treatment, 3) the powder subjected to both the mechanical energy imparting treatment and the plasma irradiation treatment, and 4) the powder subjected to the plasma irradiation treatment is excellent in all of the film thickness, Ca elution amount, and vickers hardness regardless of the particle diameter, and the order of the degree of the excellent is substantially 1) >3) >4) >5) > 6). In addition, the powder for film formation obtained by firing in an argon atmosphere as an inert gas and the hydroxyapatite powder obtained by firing in an atmospheric atmosphere were mixed in a ratio of 1: 1, when a treatment (plasma treatment) of applying plasma irradiation, a treatment of applying mechanical energy, and a treatment of applying plasma irradiation are performed, a film having a film thickness of 30 μm or more is formed, and it is found that these are effective as a powder for film formation. In addition, compared with the film formed by firing hydroxyapatite powder in an argon atmosphere, the film formed by firing hydroxyapatite powder in a 1: 1 ratio obtained by firing hydroxyapatite powder in an argon atmosphere and in an atmosphere is inferior in all items of the film thickness, the Ca elution amount, and the vickers hardness.
7-5 argon atmosphere sintering and nitrogen atmosphere sintering 1: 1 mixed hydroxyapatite powder
The hydroxyapatite powder for film formation obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill and the hydroxyapatite powder obtained by firing in a nitrogen atmosphere and pulverizing and classifying the powder by a jet mill were mixed in a ratio of 1: 1, the same test as that of 7-2 was carried out. The results on the film thickness are shown in [ Table 43] and [ Table 44], the results on the amount of Ca eluted are shown in [ Table 45] and [ Table 46], and the results on the Vickers hardness are shown in [ Table 47] and [ Table 48 ]. [ Table 43]
[ Table 44]
[ Table 45]
[ Table 46]
[ Table 47]
[ Table 48]
From the above results, it is understood that, compared with the film formation using 5) the powder subjected to the mechanical energy imparting treatment and 6) the untreated powder, the film formation using 1) the powder subjected to the plasma irradiation treatment after the mechanical energy imparting treatment, 3) the powder subjected to both the mechanical energy imparting treatment and the plasma irradiation treatment, and 4) the powder subjected to the plasma irradiation treatment is excellent in all of the film thickness, Ca elution amount, and vickers hardness regardless of the particle diameter, and the order of the degree of the excellent is substantially 1) >3) >4) >5) > 6). Further, the film formed by firing the 1: 1 mixed hydroxyapatite powder in an argon atmosphere and firing in a nitrogen atmosphere was superior to the film formed by firing the 1: 1 mixed hydroxyapatite powder in an argon atmosphere and firing in an atmospheric atmosphere in all of the film thickness, Ca elution amount, and vickers hardness, but was inferior to the film formed by firing the hydroxyapatite powder in an argon atmosphere in all of the film thickness, Ca elution amount, and vickers hardness.
7-6 film-forming hydroxyapatite powder containing silica
In the same manner as in example 2-2 above, a powder obtained by adding 1% silica powder to hydroxyapatite powder having an average particle size of 1 μm in an argon atmosphere was fired, and then pulverized and classified by a jet mill, and a film-forming powder having a particle size of 1 μm and containing silica was used to perform the same test as in example 7-2 above. The results on the film thickness are shown in [ Table 49] and [ Table 50], the results on the amount of Ca eluted are shown in [ Table 51] and [ Table 52], and the results on the Vickers hardness are shown in [ Table 53] and [ Table 54 ].
[ Table 49]
[ Table 50]
[ Table 51]
[ Table 52]
[ Table 53]
[ Table 54]
From the above results, it is understood that, compared with the film formation using 5) the powder subjected to the mechanical energy imparting treatment and 6) the untreated powder, the film formation using 1) the powder subjected to the plasma irradiation treatment after the mechanical energy imparting treatment, 3) the powder subjected to both the mechanical energy imparting treatment and the plasma irradiation treatment, and 4) the powder subjected to the plasma irradiation treatment is excellent in all of the film thickness, the Ca elution amount, and the vickers hardness regardless of the firing temperature, and the order of the degree of the excellent is substantially 1) >3) >4) >5) ═ 6). Further, the film formed by using the hydroxyapatite powder containing silica for film formation was slightly inferior in film thickness to the film formed by using the hydroxyapatite powder fired in an argon atmosphere without silica, but was excellent in Ca elution amount and vickers hardness to the same extent.
7-7 mixing hydroxyapatite powder with different particle sizes to obtain mixed powder
The hydroxyapatite powder for film formation having an average particle size of 10 μm obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill, and the hydroxyapatite powder for film formation having an average particle size of 1 μm obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill were used in a ratio of 1: 1, the same test as that of 7-2 was carried out. The results on the film formation thickness are shown in [ Table 55] and [ Table 56], and a comparison thereof is shown in [ Table 57 ]; the results on the amount of Ca elution are shown in [ table 58] and [ table 59], and a comparison thereof is shown in [ table 60 ]; the results on Vickers hardness are shown in [ Table 61] and [ Table 62], and a comparison thereof is shown in [ Table 63 ].
[ Table 55]
[ Table 56]
[ Table 57]
[ Table 58]
[ Table 59]
[ Table 60]
[ Table 61]
[ Table 62]
[ Table 63]
From the above results, it is understood that, compared with the film formation using 5) the powder subjected to the mechanical energy imparting treatment and 6) the untreated powder, the film formation using 1) the powder subjected to the plasma irradiation treatment after the mechanical energy imparting treatment, 3) the powder subjected to both the mechanical energy imparting treatment and the plasma irradiation treatment, and 4) the powder subjected to the plasma irradiation treatment is excellent in all of the film thickness, the Ca elution amount, and the vickers hardness regardless of the firing temperature, and the order of the degree of the excellent is substantially 1) >3) >4) >5) ═ 6). In addition, compared with the film formation prepared by using the hydroxyapatite powder for film formation having the average particle size of 1 μm and the average particle size of 10 μm and the powder obtained by performing the plasma irradiation treatment after the mechanical energy imparting treatment, the film formation method using the hydroxyapatite powder for film formation having the average particle size of 1 μm and 10 μm was characterized in that the ratio of 1: 1 the hydroxyapatite powder obtained by mixing and subjecting the hydroxyapatite powder to mechanical energy imparting treatment and then to plasma irradiation treatment is excellent in all items of film thickness, Ca elution amount, and vickers hardness.
From the above experimental results, it was found that by performing a treatment (plasma treatment) of performing plasma irradiation, a film-forming powder suitable for forming a film having high hardness and low solubility to acid (a film having a small Ca elution amount) in a short time was obtained. In particular, by performing a treatment (mechanical energy → plasma treatment; separate treatment) in which plasma irradiation is performed after the application of mechanical energy, a powder for film formation suitable for forming a film having higher hardness and extremely low solubility to an acid in a shorter time is obtained.
Example 8
[ hydroxyapatite powder containing color tone modifier for film formation ]
The following powders were used for film formation treatment, and the film formation thickness, Ca elution amount, and vickers hardness were measured for each sample in the same manner as in example 7: as for the powder obtained by mixing the color tone adjusting agent into the film-forming powder fired in an argon atmosphere and pulverized and classified by a jet mill in the manner shown in example 2-3, 1) a treatment of plasma irradiation after applying mechanical energy (mechanical energy → plasma treatment; separate treatment), 3) a treatment of simultaneously applying mechanical energy and plasma irradiation (mechanical energy — plasma treatment; simultaneous treatment), 4) treatment by plasma irradiation (plasma treatment), 5) treatment by applying mechanical energy (mechanical energy treatment); and 6) powders (untreated) that are subjected only to firing, pulverization, classification, mixing without plasma irradiation and/or application of mechanical energy treatment. The film thickness, Ca elution amount, and vickers hardness were measured by the same method as in example 5.
8-1 powder containing 1% by mass of titanium oxide as a color tone modifier
The powder obtained by the following mode is used for film forming: titanium oxide as a color tone modifier was added in an amount of 1 mass% to a film-forming powder obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill, and the obtained powder was subjected to the treatments 1) and 3) to 6). The results on the film thickness are shown in [ Table 64] and [ Table 65], the results on the Ca elution amount are shown in [ Table 66] and [ Table 67], and the results on the Vickers hardness are shown in [ Table 68] and [ Table 69 ].
[ Table 64]
[ Table 65]
[ Table 66]
[ Table 67]
[ Table 68]
[ Table 69]
8-2 powder containing 5% by mass of zinc oxide as a color tone modifier
The powder obtained by the following mode is used for film forming: zinc oxide as a color tone modifier was added in an amount of 5 mass% to a film-forming powder obtained by firing in an argon atmosphere and pulverizing and classifying the powder by a jet mill, and the obtained powder was subjected to the treatments 1) and 3) to 6). The results on the film thickness are shown in [ Table 70] and [ Table 71], the results on the Ca elution amount are shown in [ Table 72] and [ Table 73], and the results on the Vickers hardness are shown in [ Table 74] and [ Table 75 ]. [ Table 70]
[ Table 71]
[ Table 72]
[ Table 73]
[ Table 74]
[ Table 75]
8-3 powder of Red No. 204 as a color tone adjuster containing 0.1 mass% of a colorant
The powder obtained by the following mode is used for film forming: the film-forming powder obtained by firing in an argon atmosphere and pulverizing and classifying by a jet mill was mixed with 0.1 mass% of red color No. 204 as a color tone adjusting agent, and the obtained powder was subjected to the treatments 1) and 3) to 6). The results of the film thickness are shown in [ Table 76] and [ Table 77], the results of the Ca elution amount are shown in [ Table 78] and [ Table 79], and the results of the Vickers hardness are shown in [ Table 80] and [ Table 81 ].
[ Table 76]
[ Table 77]
[ Table 78]
[ Table 79]
[ Table 80]
[ Table 81]
Example 9
[ Properties of powder for film formation ]
In order to examine the difference in powder properties of the hydroxyapatite powder for film formation in each process, the properties of the powder for film formation were examined by a powder X-ray diffraction test and a laser raman spectroscopy analysis test.
9-1 powder X-ray diffraction test
For the following three samples, a powder X-ray diffraction apparatus (Empyrean, manufactured by PANalytical) was used to measure the target: cu, tube voltage: 45kV, tube current: 40mA, scanning range: performing a powder X-ray diffraction test under the condition that 2 theta is 5-60 degrees, wherein the sample is as follows: hydroxyapatite powder (HAP) having an average particle diameter of 1 μm manufactured in example 2-1 (only subjected to firing, pulverization, classification, mixing without plasma irradiation and/or mechanical energy application treatment); a film-forming powder having an average particle diameter of 1 μm, which was produced in example 7-2 and obtained by subjecting the hydroxyapatite powder to a mechanical energy application and then a plasma irradiation treatment; and the powder for film formation prepared in example 8-1, which was obtained by subjecting a hydroxyapatite powder for film formation containing 1 mass% of titanium oxide to a treatment of applying mechanical energy and then irradiating the hydroxyapatite powder with plasma, and which had an average particle diameter of 1 μm. The results are shown in FIG. 4. As a result, all diffraction patterns were the same, and no difference in powder was observed among these samples.
9-2 laser Raman Spectroscopy test
Since a change in crystallinity in the vicinity of the surface of the powder particles could not be confirmed by the powder X-ray diffraction test, the powder particles were examined by raman spectroscopy. The characteristics of the following five samples were examined using a laser raman spectrometer (manufactured by inviia Reflex, RENISHAW), and the samples were: the particles having an average particle diameter of 1 μm manufactured in example 7-2 were each subjected to 1) a treatment of plasma irradiation after application of mechanical energy (mechanical energy → plasma treatment; separate treatment), 3) a treatment of simultaneously applying mechanical energy and plasma irradiation (mechanical energy — plasma treatment; simultaneous treatment), 4) treatment by plasma irradiation (plasma treatment), 5) treatment by applying mechanical energy (mechanical energy treatment), and 6) powder subjected to only firing, pulverization, classification, mixing without plasma irradiation and/or treatment by applying mechanical energy (untreated).
960cm for hydroxyapatite, for the five samples mentioned above-1The change in peak intensity before and after plasma treatment was compared for the nearby peaks. Changes in the peak intensity of the laser Raman spectrum are shown in [ Table 82]]And FIG. 5. As a result, it was confirmed that the peak intensity was higher when the plasma treatment was performed than when the plasma treatment was not performed. It was confirmed that 960cm was obtained when the mechanical energy treatment and the plasma treatment were simultaneously performed-1The peak intensity in the vicinity of the peak became high, and 960cm was observed when the mechanical energy treatment was carried out and then the plasma treatment was carried out-1The peak intensity in the vicinity becomes higher. This indicates that the crystallinity of the particle surface is improved, and it is demonstrated that the composite formation of particles accompanied by high crystallization based on the mechanochemical effect by the mechanical energy and the plasma treatment occurs.
[ Table 82]
Example 10
[ multilayer film formation layer ]
A film of a crown color adjusting material (white; containing 1% titanium oxide) was formed on a glass plate, a film of a crown color adjusting material (color close to the color of a tooth; containing 5% zinc oxide) was formed as a 2 nd layer on the 1 st layer, and a film of a crown color adjusting material (transparent (as a top coat)) was formed as a 3 rd layer on the 2 nd layer, and hydroxyapatite alone was used. The film formation conditions were the same for all of the layers 1, 2 and 3, and were set to the head tip nozzle inner diameter: 1.8mm, injection pressure: 0.5 MPa. The distance between the tip of the spray nozzle and the substrate was set to 1.0mm (the tip of the spray nozzle was kept perpendicular to the substrate), and the moving speed of the spray nozzle was set to 5 mm/sec. The results (photograph) are shown in FIG. 7. Fig. 8 shows a cross-sectional image of the multilayer film-forming layer shown in fig. 7, which is obtained by a laser microscope.
The powder for film formation (containing 1% of titanium oxide; left drawing) containing the color tone adjusting agent of examples 2 to 3 was mixed with 5% of zinc oxide; right panel)) is shown in fig. 9, a photograph of a film-forming layer formed on a portion of a tooth surface under the following film-forming conditions: the inner diameter of the nozzle at the front end of the machine head is 1.8mm, the spraying pressure is 0.5MPa, the distance between the front end of the spraying nozzle and the substrate is 1.0mm (the front end of the nozzle is kept vertical to the substrate), and the moving speed of the spraying nozzle is 5 mm/s.
Industrial applicability
The film-forming powder of the present invention is useful in the field of dental treatment.
Description of the reference numerals
1 AC/DC converter of plasma generator
2 cold cathode tube inverter of plasma generator
3 boost circuit of plasma generator (Cockcroft-Walton circuit)
4 plasma nozzle of plasma generating device
5 gas flowmeter of plasma generating device
Claims (17)
1. A powder for film formation having an average particle diameter of 0.5 to 30 [ mu ] m, which is used in a device for spraying teeth and is produced by firing hydroxyapatite, fluorapatite, carbonic apatite or magnesium solid solution apatite at 600 to 1350 ℃ in an argon or nitrogen atmosphere.
2. The film-forming powder according to claim 1, further comprising a color tone adjuster for adjusting the color tone of a crown.
3. The film-forming powder according to claim 2, wherein the color tone adjuster for a dental crown is at least one selected from the group consisting of titanium oxide, zinc oxide, ultramarine blue and red pigments.
4. The film-forming powder according to any one of claims 1 to 3, wherein the film-forming powder is produced by plasma irradiation.
5. The powder for film formation according to claim 4, wherein the powder for film formation is produced by further applying mechanical energy.
6. The film-forming powder according to claim 5, wherein the film-forming powder is produced by plasma irradiation after application of mechanical energy.
7. The film-forming powder according to claim 4, wherein helium gas is used as an irradiation gas in the plasma irradiation.
8. The powder for film formation according to claim 1 or 2, wherein when the powder is sprayed onto a substrate under conditions of a nozzle inner diameter at a nose tip of 0.5 to 5.0mm, a spraying pressure of 0.2 to 0.8MPa, a distance between a nozzle tip and the substrate of 0.1 to 3.0cm, and a moving speed of the spraying nozzle of 0 to 10 mm/sec, a film formed has a film thickness of 30 μm or more and a Vickers hardness of 340Hv or more.
9. A method for producing a film-forming powder having an average particle diameter of 0.5 to 30 [ mu ] m for forming a film on a tooth surface by using the powder for film formation in an apparatus for spraying teeth, characterized by comprising firing hydroxyapatite, fluoroapatite, carbonic apatite or magnesium solid solution apatite at 600 to 1350 ℃ in an argon or nitrogen atmosphere, and then pulverizing and classifying the powder.
10. The method for producing a film-forming powder according to claim 9, further comprising blending a color tone adjuster for adjusting a color tone of a crown.
11. The method for producing a film-forming powder according to claim 10, wherein the color tone adjuster for a dental crown is at least one selected from the group consisting of titanium oxide, zinc oxide, ultramarine blue and a red pigment.
12. The method for producing a film-forming powder according to claim 9 or 10, wherein the plasma irradiation is performed after the pulverization and classification.
13. The method for producing a film-forming powder according to claim 12, further comprising applying mechanical energy.
14. The method for producing a film-forming powder according to claim 13, wherein the mechanical energy is applied and then plasma irradiation is performed.
15. The method for producing a film-forming powder according to claim 12, wherein helium gas is used as an irradiation gas in the plasma irradiation.
16. The method for producing a powder for film formation according to claim 9 or 10, wherein when the powder is sprayed onto a substrate under conditions of a nozzle inner diameter at a head tip of 0.5 to 5.0mm, a spraying pressure of 0.2 to 0.8MPa, a distance between a nozzle tip and the substrate of 0.1 to 3.0cm, and a moving speed of the spraying nozzle of 0 to 10 mm/sec, a film formed has a film thickness of 30 μm or more and a Vickers hardness of 340Hv or more.
17. A pellet comprising the film-forming powder according to any one of claims 1 to 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-139692 | 2015-07-13 | ||
| JP2015139692 | 2015-07-13 | ||
| PCT/JP2016/003297 WO2017010089A1 (en) | 2015-07-13 | 2016-07-12 | Tooth-surface-membrane-forming powder containing sintered apatite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107735070A CN107735070A (en) | 2018-02-23 |
| CN107735070B true CN107735070B (en) | 2021-04-23 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680036638.8A Pending CN107708650A (en) | 2015-07-13 | 2016-07-12 | Dental surface film formation powder comprising the apatite through burning till |
| CN201680036565.2A Active CN107735070B (en) | 2015-07-13 | 2016-07-12 | Powder for forming tooth surface film comprising calcined apatite |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680036638.8A Pending CN107708650A (en) | 2015-07-13 | 2016-07-12 | Dental surface film formation powder comprising the apatite through burning till |
Country Status (13)
| Country | Link |
|---|---|
| US (3) | US11007125B2 (en) |
| EP (2) | EP3323406B1 (en) |
| JP (2) | JP6163641B2 (en) |
| KR (4) | KR102264866B1 (en) |
| CN (2) | CN107708650A (en) |
| AU (2) | AU2016293656B2 (en) |
| CA (2) | CA2994374C (en) |
| ES (1) | ES2912114T3 (en) |
| HK (2) | HK1246198A1 (en) |
| RU (2) | RU2688152C1 (en) |
| SG (2) | SG11201710905WA (en) |
| TW (2) | TWI698408B (en) |
| WO (2) | WO2017010089A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11007125B2 (en) * | 2015-07-13 | 2021-05-18 | Kabushiki Kaisha Sangi | Tooth-surface-membrane-forming powder containing sintered apatite |
| JP6778295B2 (en) * | 2019-04-09 | 2020-10-28 | 学校法人近畿大学 | Method of immobilizing hydroxyapatite on titanium-based metal substrate and hydroxyapatite-coated metal material |
| CN110200709B (en) * | 2019-07-15 | 2021-12-14 | 杨桐 | Framework porcelain tooth veneer free of tooth preparation and preparation method thereof |
| CN110694093A (en) * | 2019-11-18 | 2020-01-17 | 袭晓冰 | Infectious department ward antiseptic solution sprinkler |
| JP7294260B2 (en) * | 2020-07-09 | 2023-06-20 | 日東紡績株式会社 | Hydroxyapatite particle dispersion and method for producing hydroxyapatite-adhered base material |
| CN112592171A (en) * | 2020-12-16 | 2021-04-02 | 昆明理工大学 | Preparation method of magnesium oxide/hydroxyapatite porous composite material |
| WO2023194316A1 (en) * | 2022-04-05 | 2023-10-12 | Ferton Holding S.A. | Powder for use in treating tooth surfaces |
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